PCI Syllabus---Distillation: Basic Principles and methodology of simple

distillation, flash distillation, fractional distillation, distillation under reduced pressure,

steam distillation & molecular distillation

DISTILLATION

Q.1. What is distillation/Define Distillation?

Distillation refers to the selective boiling and subsequent condensation of a component in
a liquid mixture. It is a separation technique that can be used to either increase the
concentration of a particular component in the mixture or to obtain (almost) pure
components from the mixture. The process of distillation exploits the difference in the
boiling points of the components in the liquid mixture by forcing one of them into a
gaseous state.

It is important to note that distillation is not a chemical reaction but it can be considered
as a physical separation process. An illustration describing the laboratory setup that is
generally used to execute this process is provided below.

Fig 1: Process of Distillation

The distillation performed on a laboratory scale often uses batches of the liquid mixture
whereas industrial distillation processes are generally continuous, requiring a constant
composition of the mixture to be maintained.
Q.2: Discuss the Raoult’s Law.

Raoult’s law states that, at any particular temperature, the partial pressure of one
component of a binary mixture is equal to the mole fraction of that component multiplied
by its vapor pressure in the pure state at this temperature.
i.e Partial vapor pressure of a liquid (pA) = vapor pressure of pure liquid (P 0A) x mole
fraction of the liquid(xA)

to illustrate Raoult’s law, let us consider the case of benzene and toluene mixture. At a
temperature of 1000C toluene has a vapor pressure of 556 mm Hg. Consequently, if
partial pressure is plotted against composition, the partial pressures of toluene at various
compositions will fall along a straight line from 556 mm for pure toluene to zero for pure
benzene. At this same temperature benzene has vapor pressure of 1350 mm, and its vapor
pressure will change linearly from zero for 0% benzene to 1350 mm for pure benzene.
The total pressure for any composition will be the sum of the two partial pressures at that
composition

If the partial pressures are straight lines i.e. Raoult’s law holds then the total pressure will
be a straight line between 556 m for pure toluene and 1350 mm for pure benzene. Ideal
solution: Ideal solution is defined as a solution that obey’s Raoult’s law. Examples: In
these solutions the components have similar structures e.g. benzene and toluene system,
n-heptane and n-hexane, ethyl bromide and ethyl iodide etc.
 In this case total pressure is equal to sum of the partial pressures of the components, i.e.
P = (pA + pB )
 The total pressure curve will be a straight line.
Non-ideal or real solutions Solutions those will not obey Raoult’s law are known as non-
ideal or real solutions. Most real solutions shows deviation. The deviations are observed
due to uneven solute-solute, solute-solvent and / or solvent-solvent interactions. Two
types of deviations are found:

1. Positive deviation
In these systems the overall vapor pressure is greater than the sum of the partial vapor
pressures of the individual components, i.e. P > (pA + pB ) When the components differ
in their polarity, length of carbon chain or degree of association, the system may show
positive deviation. Examples: Carbon tetrachloride and cyclohexane, benzene and
ethanol.
2. Negative deviation
In these systems the overall vapor pressure is lower than the sum of the partial vapor
pressures of the individual components, i.e. P < (pA + pB ) If hydrogen bonding, salt
formation and hydration occurs then these systems may show negative deviation.
Examples: Chloroform and acetone, pyridine and acetic acid, water and nitric acid.
Applications of Raoult's Law:
Predicting boiling and freezing points of solutions:
Knowing the mole fraction of a solute, we can calculate the change in boiling and
freezing points of a solution compared to the pure solvent. This is crucial in various
industrial processes and scientific experiments.
Concentration determination:
By measuring the vapour pressure lowering of a solution, we can indirectly determine the
concentration of the solute. This technique is used in analytical chemistry and
pharmaceutical applications.
Understanding osmosis and separation processes:
Raoult's law plays a vital role in comprehending osmotic pressure, a key factor in various
separation techniques like reverse osmosis and dialysis.

Limitations of Raoult’s Law

 Raoult's law works well for ideal solutions, where the gas phase behaves like a
mix of ideal gases. But ideal solutions are uncommon and hard to find.
 Chemical components in ideal solutions must be identical.
 In real-life mixtures, liquids often don't have the same attractive forces, causing
deviations from Raoult's law.
 This means the actual behavior of the solution might not match what Raoult's law
predicts.
Q.3.Expalin distillation without rectification
OR
Explain equilibrium and Differential distillation? Equilibrium distillation
There are two important types of distillation that do not involve rectification. The
first of these is equilibrium or flash distillation and the second is simple or differential
distillation.
*What is it - Equilibrium distillation involves vaporizing a definite fraction of a
batch of liquid, keeping all the liquid and the entire vapor in intimate contact so that at
the end of the operation the vapor is in equilibrium with the liquid withdrawing the vapor,
and condensing it. The relationship between liquid and vapor compositions at the end of
the process is, therefore, that exhibited by equilibrium diagram.
*How is it done - Consider a binary system whose components are A and B. A is
the more volatile component. Let the number of moles in the initial batch be Wo, and let
the composition of the original batch, expressed as mole fraction of component A, be xo.
Suppose that V moles are vaporized in an equilibrium-distillation process. Then there
will be left in the liquid state (Wo - V) moles. Let the composition of the residual liquid be
x, and the composition of the vapor be y. Since there were Woxo moles of more volatile
component in the original liquid, and since none of this has been lost, this quantity must
equal the sum of the amounts of volatile component in the final liquid and vapor:

Woxo = Vy + (Wo - V)x (1)

This equation is a material balance of the more volatile component. There are two
unknowns in Eq. (1). These unknowns are x and y. Before the equation can be solved
numerically, the value of x and y are found from the equilibrium curve of x and y *
*Applications--Equilibrium distillation is not of great importance in the handling of two-
component systems. The method is used in multicomponent systems in oil refining,
however, where petroleum mixtures are heated under pressure in pipe stills, the pressure
removed, and the vapor flashed under approximately equilibrium conditions from the
superheated liquid.
Differential distillation-
*What is it? - In differential, or simple, distillation the vapor generated by boiling the
liquid is withdrawn from contact with the liquid and condensed as fast as it is formed.
*How is it done- Consider a batch of Wo moles of liquid. Suppose that at any given time
during the distillation there are W moles of liquid left in the still. At this time let the
liquid composition be x and the vapor composition y. The total amount of component A
in the liquid will be xW. Suppose a very small amount of liquid dW is vaporized. During
the vaporization the liquid composition will diminish from x to x – dx, and the weight of
the liquid will diminish W to W – dW. There will be left in the still (x – dx) (W – dW)
moles of A, while the amount y dW has been removed from the still. A material balance
equation with respect to component A is, therefore,

xW = (x – dx) (W – dW) + y dW (2)

Expanding Eq. (2)

xW = xW – xdW + dxdW – W dx + y dW (3)

I twill be noted that there is a second-order differential in Eq. (3) which may be
neglected, and the equation my be written as
dW = dx (4)
W y–x
Equation (5) is integrated between the limits of Wo, the initial weight in moles, and W1,
the final weight in moles, on the left-hand side, and between the limits xo, the initial
concentration, and x1, the final concentration, on the right-hand side, Eq. (5) results:

∫ dW = ln Wo = ∫ dx (5)
W W1 y–x
Equation (5) is known as the Rayleigh Equation. x and y can be obtained from
equilibrium curve, since this curve gives the relationship between x and y.
Simple or differential distillation is done by commercial batch-distillation processes
where the vapor is removed as fast as it is formed without much condensation. Although
as a method of separation this process is not effective, many such stills are used,
especially where the components to be separated have widely different boiling points and
methods giving sharp separations are not necessary.
* Examples of differential distillation -The older design of the batch type of petroleum
still, known as the “toping” still, is an example. Also, laboratory distillations carried on
without reflux columns are of this type.

Q.4. Explain with diagram what is rectification?

 Introduction-Rectification, the method of distillation that has been highly developed
and is now the most commonly used method for separation.
Construction and working-A rectifying unit is shown diagrammatically in Fig. 2

Fig 2: Process of rectification

It consists primarily of
(a) a still or reboiler, in which vapor is generated,
(b) a rectifying or fractionating column through which this vapor rises in counter-current
contact with a descending stream of liquid, and
(c) a condenser, which condenses all the vapor leaving the top of the column, sending
part of this condensed liquid (the reflux) back to the column to descend counter to the
rising vapors, and delivering the rest of the condensed liquid as product. As the liquid
stream descends/ goes down the column it is progressively enriched with the high-boiling
constituent (less volatile component) and as the vapor stream ascends it is progressively
enriched with the low-boiling constituent (more volatile component). The column then
becomes an apparatus for bringing these streams into intimate contact, so that the vapor
stream tends to vaporize the low-boiling constituent from the liquid, and the liquid stream
tends to condense the high-boiling constituent from the vapor. The top of the column is
cooler than the bottom, so that the liquid stream becomes progressively hotter as it goes
down and the vapor stream becomes progressively cooler as it rises. This heat transfer is
accomplished by actual contact of liquid and vapor; and for this purpose, effective
contacting is desirable within the rectifying column.
Q.5.Explain the Concept, theory, procedure and uses of Steam distillation?

Theory of Steam distillation-

Vapor pressure of Immiscible liquids-
In a pair of immiscible liquids each liquid exerts its own vapor pressure and
neither liquid has any appreciable effect on the vapor pressure of the other. The vapor
pressure of the mixture at a given temperature is equal to the sum of the vapor pressure of
the two pure components at that temperature.
Completely immiscible liquids are not known but very slightly soluble can be
considered to be immiscible.
e.g. Turpentine + Water
Toluene + Water
Volatile oils + Water
Principle:
 The principle behind steam distillation is a way of separating miscible liquid based on
their volatilities.
 The boiling point of the products is so minimized that it permits the constituents to get
vaporized.
Construction:
 The general assembly of laboratory scale vacuum distillation units.
 It consists of a metallic can to generate steam.
 This metallic can is fitted with a cork having two holes.
 A safety tube is passed through one of the holes and a bent tube is passed through the
other.
 The safety tube should reach almost the bottom of the flask.
 In case the pressure inside the steam generator becomes too much, water will be forced
out of the safety tube and the pressure will be released.
 When steam starts coming out from the safety tube; it indicates that the steam can is
almost empty.
 The other end of the bent tube is connected to the flask containing non-aqueous liquid
(for example, turpentine) through a rubber bung.
 This tube should reach almost the bottom of the flask.
 The flask is connected to a condenser through a delivery tube as shown in the Fig. 3
 The condenser is connected to a receiver flask using an adaptor.
 The steam can and flask are heated by a suitable method.
 Fig: 3 Steam Distillation
Methodology (Working):
 The non-aqueous liquid or oil to be purified or extracted is placed in the flask.
 A small quantity of water is added to it.
 Fill the steam can with water.
 The steam can and the flask are heated simultaneously.
 The steam generated in the steam can pass to the flask through the bent tube.
 A uniform flow of steam passes through the boiling mixture in the flask.
 The mixture gets heated.
 The steam carries the volatile oil and passes into the condenser.
 Cool water passes through the condenser.
 The condensed liquid is collected into the receiver as distillate.
 The distillate is the mixture of immiscible liquids.
 The immiscible liquids form separate layers which can be easily separated using a
separating flask.

Distillation of Immiscible liquids-

A mixture of immiscible liquids begins to boil when the sum of their vapor
pressures is equal to the atmospheric pressure. Thus in the case of water and a liquid
which boils at a much higher temperature than water, the mixture boils below the boiling
point of pure water. The boiling point of turpentine is about 160 oC but when it is mixed
with water and heated, the mixture boils at about 95.6 oC. At this temperature the vapor
pressure of water is 647 mm and that of turpentine is 113 mm. The sum, 647 + 113 = 760
mm which is normal atmospheric pressure. From these facts, it will be sum that a high
boiling point substance may be distilled with water at a temperature much below its
boiling point.
For substances which are insoluble in water and not decomposed by it, this
provides an alternative to distillation under reduced pressure. The composition of the
vapors over a pair of immiscible liquids may be calculated approximately from the vapor
pressure and molecular weights of the components. Since in distillation this vapor is
condensed, this also represents the composition of the distillate. If the vapor pressure of
the two components at the boiling point of mixture are P 1 and P2, by Avogadro’s
hypothesis, the number of molecules present in the vapor is proportional to the vapor
pressure, P1 and P2.
The weights of the components in the vapor will therefore be in the ratio, P 1M1:
P2M2, where M1 and M2 are respective molecular weights.
Hence, the proportion W1, W2 of the two components in distillate is given by the
equation:
W1 = P1M1
W2 P2M2
Turpentine has molecular weight 136 and molecular weight of water is 18. The
boiling point of this mixture is 95.6 oC and vapor pressures are turpentine 113 and water
647.
Therefore—
113 + 647 = 760
and the distillate will contain turpentine and water in the ratio of
113 × 136: 18 × 647 or 1:32:1.
From these calculations, it can be seen that a substance of low volatility or high
boiling can be satisfactory distilled in steam provided its molecular weight is very high
than that of water.
Water is particularly considered suitable for steam distillation because it has low
molecular weight and high boiling point.
Large Scale Apparatus-

Fig: 4 Large Scale Steam Distillation

Steam distillation is used to extract most of the volatile oils such as clove, eucalyptus etc.
A common form of water still is shown diagrammatically. A still of this type has a jacket
for heating. Live steam is injected below the material which is supported on a perforated
false bottom. The vapor generated is run through a cooling coil and the distillate comes
out in a receiver. Oil forms an upper layer and water lower. Water can be run out and
returned to still for heating or can be run to waste and oil which collects on surface is run
off and collected. Some volatile oils are heavily than water in such cases the operation is
reversed.

Q.6. Basic Principles, Construction, Working, Application, Advantages and

disadvantages of following:
1. Simple Distillation
2. Flash Distillation
3. Fractional Distillation

1. Simple Distillation:
 Simple distillation is the most basic type of distillation.
 Simple distillation is a unit operation in which two liquids with different boiling
points are separated.
Principle:
 This process can be repeated until all the fractions of the original mixture are
separated. In order for simple distillation to perform, the two liquids’ boiling points
must have a difference of at least 25 °C (or about 77 °F).
 Simple distillation is a process of heating and cooling liquids in order to separate
and purify them. As the liquid being distilled is heated, the vapours that form are
richest in the component of the mixture that boils at the lowest temperature.
 Purified component boils, and thus turns into vapours, over a relatively small
temperature range (2 or 3 °C).
Working of Simple Distillation
1. Calibration of thermometer: Calibration can be done by placing the thermometer
in an ice bath of distilled water. Allow the thermometer to reach thermal equilibrium.
Now remove from ice water and place it in a beaker of boiling distilled water and
again allow it to reach thermal equilibrium. If the temperatures measured does deviate
from the expected values by more than two degrees then use it for recording
temperature in the distillation process.
2. Filling the distillation flask: The flask is filled with not more than two-thirds of
its volumes to have sufficient space above the liquid surface so that when boiling
begins the liquid will not be propelled into the condenser. This is important in the
viewpoint of the purity of the distillate. Porcelain chips should be placed in the
 distillation flask to prevent superheating of the liquid and to cause a more controlled
boiling, eliminating the possibility of liquid bumping into the condenser.
3. Heating the distillation flask: The distillation flask is heated slowly until the
liquid begins to boil. The vapours rise through the neck of the distillation flask and
pass through the condenser and condense and drip into the collection receiver, Fig.1.
Generally, the rate of distillation is approximately 20 drops per minute. Distillation
must occur slowly enough that all the vapours condense to liquid in the condenser.
Many organic compounds are flammable and if vapours pass through the condenser
without condensing, they may ignite as they come in contact with the heat source.
4. Condensation of vapours: As the distillate begins to drop from the condenser, the
temperature changes steadily. When it is stable, a new receiver is used to collect all
the drops that form over a two to a three-degree range of temperature. As the
temperature begins to rise further, a third receiver is used to collect the distillate. This
process is repeated; using a new receiver every time the temperature stabilizes or
begins changing until all of the distillate has been collected in discrete fractions. All
fractions of the distillate should be saved until it is shown that the desired compound
has been effectively separated by distillation.

Fig: 5 Simple Distillation

Advantages:
 It is simple, cheap, easy and economic method.
 It requires less energy.
 This process requires single run and thus is comparatively faster.
Disadvantages:
 The final product may contain impurities.
 Azeotropic mixtures cannot be separated by simple distillation.
 Not suitable for mixtures containing thermolabile components.
 The volume of mixture should be not more than 2/3rd of the container.
Applications:
 Simple distillation is primarily used for production of distilled water.
 Many volatile oils are separated by simple distillation.
 It is also used in the separation of organic solvents from mixtures.
 It is used to separate non-volatile components from volatile ones.
 It is used in preparing pharmaceutical spirits

2. Flash distillation
Principles:
Flash distillation is a separation process that is based on flash vaporization. In this
process, a hot liquid mixture passes from a high-pressure zone to a low-pressure zone,
causing it to suddenly vaporize. The reduced pressure lowers the boiling point of the
liquid, leading to its vaporization. This process is used to separate components of a
mixture based on their boiling points.
Methodology of Flash Distillation:
 The Flash distillation unit consists of a pump attached to the feed tank from where it
pumps feed at high pressure. This unit has a heating chamber through which the liquid
mixture carrying pipe passes.
 The chamber is insulated to avoid heat loss during operation and maintain the desired
temperature.
 There is a pressure control valve fitted between the heating chamber and the flash drum.
 The other end of the pipe directly opens into the flash drum. In single-stage flash
distillation unit, liquid outlet is provided at the bottom. In case of multi stage distillation,
the liquid and vapours are taken to the next unit for further distillation.
 When designing a flash system it is important to provide enough disengaging space in
the flash drum. Flash drum can also be designed as cyclone separators.
Applications:
 It is used in the petroleum industry for refining crude oil.
 It is used in the desalination of ocean water by multi-stage flash distillation.
 It can also be used for separation of heptane from octane.
 Fig: 6 Flash Distillation

Advantages:
 It is a continuous process.
 The equipment is smaller than the multi-stage flash distillation.
 The operating costs are low compared to multi-stage flash distillation.
Disadvantages:
 It is not effective in separating components of comparable volatility.
 It is not suitable for two-component systems.

3. Fractional Distillation
Principles:
 The basic principle of this type of distillation is that different liquids boil and
evaporate at different temperatures. When the mixture is heated, the substance with
the lower boiling point starts to boil first and convert into vapors
Methodology of fractional distillation:
 The methodology of fractional distillation involves repeated distillations and
condensations. The process requires a few fractional distillation apparatuses,
including a distilling flask, condenser, receiver, fractionating column, thermometer,
and heat source.
 After setting up the apparatus, a mixture of two miscible liquids A and B is taken,
where A has more volatility than substance B.
 The solution is added into the distilling flask while the fractionating column is
connected at the tip of the flask.
  Heat is applied, which increases the temperature slowly. The mixture then starts to
boil and vapors start rising in the flask. The vapors are from the volatile component
A.
 The vapors then start moving through the fractionating column into the condenser
where it is cooled down to form a liquid which is collected in the receiver.
 Throughout the process, vaporization and condensation take place repeatedly until
the two mixtures are separated completely

Fig: 7 Fractional Distillation

Q.7. Explain the Concept, theory, methodology, application, advantages and

disadvantages of Distillation Under Reduced Pressure?

Vacuum Distillation Principle:

 This distillation method works on the principle that boiling occurs when the vapour
pressure of a liquid exceeds the ambient pressure. Vacuum distillation is used with or
without heating the mixture.
Construction:
 The vacuum distillation unit consists of a distillation column, condensing distillate, and
reboiler.
 Vacuum pumps and vacuum regulators are added to distillation columns to maintain the
column at a vacuum. Many mixtures can be distilled at much more economical
temperatures with the use of these vacuum distillation columns.
Methodology (Working):
A vacuum distillation is also called as low temperature distillation. The target product in
this distillation could either be the remaining product, the distilled product or a purified
product. The vacuum pressure associated with a distillation depends on the product to be
distilled. For example, volatile substances like those used in oil refineries are likely to
undergo vacuum distillations at above 1 Torr, perhaps 20-50 mmHg.

Fig: 8 Vacuum Distillation

Applications:
 The products of normal distillation are further distilled using vacuum distillation.
 The high boiling point hydrocarbons, such as lubricants and waxes, are separated at
economical temperatures.
 Vacuum distillation is also used in the separation of sensitive organic chemicals and
recovery of organic solvents.
Advantages:
 Vacuum distillation reduces the number of stages needed in distillation.
 The product output per day is very high. It requires lower temperatures at lower
pressures.
 It has very high capacity to handle liquid mixtures giving high yield and highest purity.
 Vacuum distillation can improve a separation by prevention of product degradation
because of reduced pressure leading to lower tower bottoms temperatures.
Disadvantages:
 High energy costs of vacuum pumps.
 Pressure and energy losses due to any leaks or cracks.
 Large column diameters needed for the process to be efficient.

Q.8. Explain the Concept, theory, methodology, application, advantages and

disadvantages of Molecular Distillation?

Principle:
 Molecular distillation is considered as the safest mode of separation and to purify the
thermally unstable molecules and related compounds with low volatility and elevated
boiling points.
 The process distinguishes the short residence time in the zone of the molecular
evaporator exposed to heat and low operating temperature due to vacuum in the space of
distillation.
Mean free path: It is defined as the average distance travelled by single molecules in a
straight line without any collision

Construction of Molecular Distillation:

 A simple molecular distillation has a unit that is placed on a hot surface. The distillate
moves a very short distance before it gets condensed.
 If the substance is not too viscous, it will drip from the point on the glass condensing
surface and run down to the receiving point.
 The sophisticated apparatus with a different design will have the liquid distilled down
on a heated surface close to the condenser.
 The movement of a film prevents a build-up of non-volatile materials on the surface of
the material to be distilled as this might cause the distillation to stop.
 Fig: 9 Molecular Distillation

Working of Molecular Distillation:

 The molecular distillation process is carried out at very low pressure so that the
distance between the hot and condensing surface is less than the mean free path of the
molecules. Each of the units is a single-stage but has several units in series.
 Molecular distillation is applied to thermally sensitive high molecular weight materials.
 The contact times in commercial units may be low as 0.001 seconds. The film thickness
is of the order of 0.05 – 0.1 mm.
 In vacuum operations, air ingress is very much possible, whereas in pressure operations
vapor emissions are likely to occur.
 The distillation process is inherently hazardous with flammables and the presence of a
huge volume of flammables in reboilers, in column internals and adjacent piping pose
huge explosion hazards in these distillation units.
 The concentration gradient between the top and bottom of the column has a bearing on
safety.
 The concentration of impurities in the column can lead to hazards.

Advantages of Molecular Distillation

 Toxicity: Avoids the problem of toxicity of solvents used as the separating agent.
 Thermal stability: Minimizes losses due to thermal decomposition.
 Continuous process: It can be used in a continuous feed process to harvest distillate
without having to break the vacuum.
 Stability: The vacuum allows oils to be processed at minimal temperatures, reducing the
risk of oxidative damage.
 Purity: Separating the oil’s components by weight allows contaminants to be reduced
far below industry standards.
Disadvantages of Molecular Distillation
 Cost: The cost for this complicated technology is relatively high.
 Natural form: The starting natural triglyceride form is lost in the distillation process.
Applications of Molecular Distillation
 It is used for the separation of vitamins and polyunsaturated fatty acids.
 Molecular distillation is used industrially for the purification of oils.
 It is also used to enrich borage oil in γ-linolenic acid (GLA) and recover tocopherols
from deodorizer distillate of soybean oil. It can be used for the production of synthetic
and natural vitamin E,
 Capsicum red pigment containing 1% to 2% of the solvent can be separated after two-
stage molecular distillation.
 It is used for the separation of strong spices like volatile substances.
 It is used for highly heat-sensitive materials.

Q.9. Explain the Concept of Centrifugal Molecular Distillation?

Fig: 10 Centrifugal Molecular Distillation

 Vacuum is applied at the center of vessel then rotate on high speed

 Now feed is introduced into centre of vessels through feed inlet.
 Due to high-speed rotation centrifugal force create, due to centrifugal force liquid
move outward over the surface of bucket and form a film.
 The vapour molecules moves its mean free path then it strikes the condenser then
product inlet.
  Residue is collected through residue outlet and re-circulated through feed